Search Results (3,515)

Cancer remains a leading global cause of death, with conventional treatments often limited by toxicity and recurrence. Recent advances in gene therapy and nanodrug delivery offer new avenues for precision oncology. Human telomerase reverse transcriptase (hTERT) and glutathione peroxidase 4 (GPX4) are overexpressed in many cancers and linked to apoptosis and ferroptosis, respectively. Here, we developed a manganese dioxide nanosheet (MnO₂-NS) probe co-loaded with antisense oligonucleotides targeting hTERT and GPX4 mRNA to synergistically down-regulate both genes and induce dual cell death pathways. The probe, assembled via adsorption of fluorescently labeled antisense strands, showed controllable release in the presence of glutathione (GSH). Cellular uptake and antisense release were confirmed in multiple cancer cell lines. The MnO₂-NS probe significantly suppressed cell proliferation, outperforming single-target or carrier-only controls. Molecular analyses confirmed reduced hTERT and GPX4 expression, along with GSH depletion, ROS accumulation, and elevated lipid peroxidation—collectively promoting enhanced cancer cell death. In summary, this MnO₂-NS-based co-delivery system enables synergistic gene silencing and GSH depletion, enhancing antitumor efficacy and providing a promising strategy for multifunctional nanotherapy. Full article

Polymetallic nodules enriched in Mn, Ni, Cu, Co, and other metals may be one of the first seabed mineral resources to be exploited. Although optical imagery is crucial for resource evaluation, semi-buried nodules are frequently overlooked. To address this, we propose a framework that integrates the elliptic approximation method (EAM) and the contour interweaving method (CIM) to reconstruct three types of semi-buried nodules segmented by U-Net: edge-buried, partition-buried, and almost-completely-buried. This strategy introduced a decision-making mechanism based on category fusion, which significantly enhanced the robustness and practicality of the reconstruction. Performance was assessed using four metrics: area ratio, absolute percentage change, intersection-over-union, and Chamfer distance. Among 1785 samples, the EAM recovered up to 41.8% of lost area, which substantially improved the minimum values of area ratio and intersection-over-union, and it performed well on almost-completely-buried nodules. The CIM achieved median area ratio and intersection-over-union values of 99.37% and 93.36%, respectively, and excelled in edge-buried and partition-buried types. Fusion experiments demonstrated the complementary strengths of both approaches: 23.96% of buried area was recovered in large-scale imagery recognized by U-Net. The proposed framework balances accuracy, adaptability, and computational efficiency, which enables real-time nodule identification on platforms with limited resources such as autonomous underwater vehicles. This could provide more direct support for resource evaluation and mining applications. Full article

The article presents an extensive review of modern technological solutions for pulverized coal combustion, with emphasis on combustion modifiers and biomass co-firing. It highlights the role of coal in the national energy system and the need for its sustainable use in the context of energy transition. The pulverized coal combustion process is described, along with factors influencing its efficiency, and a classification of modifiers that improve combustion parameters. Both natural and synthetic modifiers are analyzed, including their mechanisms of action, application examples, and catalytic effects. Special attention is given to the synergy between transition metal compounds (Fe, Cu, Mn, Ce) and alkaline earth oxides (Ca, Mg), which enhances energy efficiency, flame stability, and reduces emissions of CO, SO₂, and NO_x. The article also examines biomass-coal co-firing as a technology supporting energy sector decarbonization. Co-firing reduces greenhouse gas emissions and increases the reactivity of fuel blends. The influence of biomass type, its share in the mixture, and processing methods on combustion parameters is discussed. Finally, the paper identifies directions for further technological development, including nanocomposite combustion modifiers and intelligent catalysts integrating sorption and redox functions. These innovations offer promising potential for improving energy efficiency and reducing the environmental impact of coal-fired power generation. Full article

The Sichuan–Yunnan–Guizhou Pb-Zn metallogenic belt (SYG metallogenic belt), a crucial metallogenic unit on the southwestern margin of the Yangtze Block, is a key part of the South China low-temperature metallogenic domain. The incorporation mechanisms and distribution of trace elements (e.g., Ge, Ga, Cd) widely enriched in Pb-Zn sulfides throughout this region remain poorly understood. This study investigates main-ore-stage sulfides (sphalerite and pyrite) from the Maoping Pb-Zn deposit using in situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses and mapping to systematically elucidate the partitioning and occurrence of these trace elements. The key findings are as follows: (1) Sulfides show distinct elemental partitioning: sphalerite preferentially concentrates Cd, Ag, Ge, Ga, and Se, whereas pyrite is significantly enriched in Mn, Ni, As, and Co. (2) Sphalerite is the primary host for many trace elements. Cadmium, Ge, Mn, Cu, and Ag mainly enter the sphalerite lattice by substituting for Zn²⁺. Coupled substitution mechanisms, such as Zn²⁺ ↔ Cd²⁺, 2Zn²⁺ ↔ Ge²⁺ + Cu²⁺, and 2Zn²⁺ ↔ Ga³⁺ + Cu⁺, facilitate the incorporation of Ge and Ga. (3) The sphalerite exhibits a trace element assemblage of high Cd-Ge and low Fe-Mn, which is geochemically similar to typical Mississippi Valley-type (MVT) deposits and differs significantly from sedimentary exhalative (SEDEX) and magmatic–hydrothermal deposits, indicating a medium- to low-temperature metallogenic environment. Based on these geochemical signatures and epigenetic textures, we confirm that the Maoping Pb-Zn deposit exhibits similarities with MVT deposits. Nevertheless, distinct differences in the tectonic setting and metal grades suggest it is a unique SYG-type Pb-Zn deposit. Full article

In this work, a method for leaching black mass from spent Li batteries using oxalic acid was developed and experimentally verified with the objective of selectively separating lithium and cobalt. Oxalic acid proved to be an efficient and selective leaching agent. Under 1 M C₂H₂O₄, 120 min, L:S = 20, 80 °C and 300 rpm, a lithium yield of 90% was achieved, while cobalt dissolution remained low at 1.57%. Subsequently, cobalt spontaneously precipitated from the leachate within several hours, and the solid phase was fully separated after 24 h. The leachate contained minor amounts of accompanying metals, with dissolution yields of 0.5% Mn, 8% Fe and 1.4% Cu. These impurities were removed from the leachate by controlled pH adjustment using NaOH at ambient temperature and 450 rpm, with complete precipitation at pH 12. This procedure generated a purified lithium-rich leachate, which was converted into lithium oxalate by crystallisation at 105 °C. Subsequent calcination of the resulting solid at 450 °C for 30 min produced Li₂CO₃ with a purity of 91%. Based on the experimental findings, a conceptual technological process for selective lithium leaching using oxalic acid was proposed, demonstrating the potential of this method for sustainable lithium recovery. Full article

D-Tagatose is a rare sugar of interest as a low-calorie sweetener, and enzymatic isomerization of D-galactose is a practical production route. L-arabinose isomerase (L-AI; EC 5.3.1.4) is a promising catalyst for the above process, but many characterized L-AIs perform best at alkaline pH and high temperature and often require substantial divalent metal supplementation (e.g., Mn²⁺/Co²⁺), which complicates food-grade processing. Lactic acid bacteria (LAB) are attractive sources of food-compatible enzymes, yet structural information for LAB-derived L-AIs has been limited. Here, we report the 2.6 Å X-ray crystal structure of L-AI from Latilactobacillus sakei 23K (LsAI) and define its oligomeric assembly. Although the asymmetric unit contains a single monomer, crystallographic symmetry reconstructs a D₃-symmetric homohexamer composed of two face-to-face trimers, consistent with a higher-order assembly in solution. Interface analysis shows predominantly polar interaction networks, and normalized B-factor mapping reveals localized flexibility near active-site-proximal regions. These findings provide a structural basis for understanding LAB-derived L-AIs and support structure-guided engineering toward food-grade, low-metal biocatalysts for rare-sugar production. Full article

Tungsten is a critical metal for advanced industrial applications, yet its supply is challenged by the depletion of high-grade ores. This study presents a comprehensive optimization and mechanistic analysis of the alkaline fusion process for extracting tungsten from wolframite ((Fe,Mn)WO₄) using sodium carbonate (Na₂CO₃). Experimental investigations systematically evaluated the effects of alkali-to-ore ratio, reaction temperature (650–1000 °C), and reaction duration (30–270 min). Optimal conditions were established at a 2:1 Na₂CO₃-to-ore molar ratio, a reaction temperature of 750 °C, and a holding time of 30 min, achieving a tungsten extraction efficiency exceeding 99.9%. This represents a significant improvement in energy and process efficiency over conventional methods. A novel kinetic analysis reveals a two-stage reaction mechanism, transitioning from a slow, diffusion-controlled solid-state reaction (E_a = 243 kJ/mol) to a rapid, autocatalytic liquid-phase reaction (E_a = 212 kJ/mol) upon the formation of a Na₂WO₄–Na₂CO₃ eutectic above approximately 590 °C. The optimal temperature of 750 °C is rationalized as the point that ensures operation within this kinetically favorable liquid-phase regime. Furthermore, a thermochemical analysis of ore impurities indicates that silicon, lead, sulfur, and calcium are effectively sequestered into the slag phase as stable silicates, insoluble lead compounds, and sulfates, highlighting an intrinsic purification benefit. X-ray fluorescence (XRF) and X-ray diffraction (XRD) analyses confirmed minimal residual tungsten in the processed slag. This streamlined process, supported by a robust mechanistic understanding, reduces alkaline consumption, shortens reaction times, and maintains high yields, offering a sustainable and efficient pathway for leveraging declining wolframite resources. Full article

Metal pollution from metallurgical emissions poses serious environmental and public health risks in Kazakhstan. A replicated pot-culture experiment (n = 4) in a completely randomized design under controlled phytotron conditions evaluated biomass production and metal accumulation in six crop and forage species, alfalfa (Medicago sativa), amaranth (Amaranthus spp.), corn (Zea mays), mustard (Brassica juncea), rapeseed (Brassica napus), and sunflower (Helianthus annuus); three ornamental species, purple coneflower (Echinacea purpurea), marigold (Tagetes spp., ‘Tiger Eyes’), and sweet alyssum (Lobularia maritima); and three native wild plants, greater burdock (Arctium lappa), horse sorrel (Rumex confertus), and mug wort (Artemisia vulgaris). Plants were grown in soils collected from the Qarmet industrial zone in Temirtau, central Kazakhstan. Initial soil analysis revealed substantial mixed-metal contamination, ranked as Mn > Ba > Zn > Sr > Cr > Pb > Cu > Ni > B > Co. Mn reached 1059 mg·kg⁻¹, ~50-fold higher than B (22.7 mg·kg⁻¹). Ba (620 mg·kg⁻¹) exceeded FAO/WHO limits sixfold, Zn (204 mg·kg⁻¹) surpassed the lower threshold, and Pb (41.6 mg·kg⁻¹) approached permissible levels, while Cr, Cu, Ni, Co, and Sr were lower. Biomass production varied markedly among species: corn and sunflower produced the highest shoot biomass (126.8 and 60.9 g·plant⁻¹), whereas horse sorrel had the greatest root biomass (54.4 g·plant⁻¹). Root-to-shoot ratios indicated shoot-oriented growth (>1–8) in most species, except horse sorrel and burdock (<1). Metal accumulation was strongly species-specific. Corn and marigold accumulated Co, Pb, Cr, Mn, Ni, Cu, B, and Ba but showed limited translocation (transfer function, TF < 0.5), whereas sunflower, amaranth, and mug wort exhibited moderate to high translocation (TF > 0.8 to <1) for selected metals. Corn is recommended for high-biomass metal removal, marigold for stabilization, sunflower, horse sorrel, and mug wort for multi-metal extraction, and amaranth and coneflower for targeted Co, Ni, and Cu translocation, supporting sustainable remediation of industrially contaminated soils. Full article

Background: Solid microneedles (MNs) are effective transdermal delivery devices but are commonly fabricated from metallic or non-biodegradable materials, raising concerns related to sustainability, waste management, and processing constraints. This study aimed to evaluate the suitability of the biodegradable biopolyester poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (PHBHVHHx) as a structuring material for solvent-free fabrication of solid MN arrays and to assess their mechanical performance, insertion capability, and drug delivery potential. Methods: PHBHVHHx MN arrays were fabricated by solvent-free micromolding at 200 °C. The resulting MNs were morphologically characterized by scanning electron microscopy. Mechanical properties were assessed by axial compression testing, and insertion performance was evaluated using a multilayer Parafilm skin simulant model. Diclofenac sodium was used as a model drug and applied via surface coating using a FucoPol-based formulation. In vitro drug release was assessed in phosphate-buffered saline under sink conditions and quantified by UV–Vis spectroscopy. Results: PHBHVHHx MN arrays consisted of sharp, well-defined conical needles (681 ± 45 µm length; 330 µm base diameter) with micro-textured surfaces. The MNs withstood compressive forces up to 0.25 ± 0.03 N/needle and achieved insertion depths of approximately 396 µm in the Parafilm model. Drug-coated MNs retained adequate mechanical integrity and exhibited a rapid release profile, with approximately 73% of diclofenac sodium released within 10 min. Conclusions: The results demonstrate that PHBHVHHx is a suitable biodegradable thermoplastic for the fabrication of solid MN arrays via a solvent-free process. PHBHVHHx MNs combine adequate mechanical performance, reliable insertion capability, and compatibility with coated drug delivery, supporting their potential as sustainable alternatives to conventional solid MN systems. Full article

The South Sakhalin mud volcano (Sakhalin Island, Russia) emits HCO₃-Cl/Na-Mg water, emanates CO₂ prevailing over CH₄ in the gas phase, and extrudes mud bearing five carbonate mineral species. The study focuses on the distribution, diversity, and origin of the carbonate minerals from the mud volcano (MV) ejecta, in terms of carbon cycle processes. The data presented include a synthesis of field observations, compositions of MV gases and waters, chemistry of carbonate minerals, as well as stable isotope geochemistry of MV waters (δ¹³C, δD, and δ¹⁸O) and carbonates (δ¹³C and δ¹⁸O). The sampled MV waters are isotopically heavy, with δ¹⁸O = +5.7‰ to +7.5‰ VSMOW, δD = −18.0‰ to −11.0‰ VSMOW, and ¹³C (δ¹³C_DIC = +6.9‰ to +8.1‰ VPDB). This composition may be due to the dilution of basinal water with dehydration water released during the diagenetic illitization of smectite. Carbonates in the sampled mud masses belong to three genetically different groups. Mg-rich siderite, (Fe_0.54–0.81Mg_0.04–0.30Ca_0.05–0.23Mn_0.00–0.08)CO₃, disseminated in abundance throughout the mud masses, coexists with common calcite and sporadic ankerite. The trace-element chemistry of Mg-siderite, as well as the oxygen (δ¹⁸O = +34.4‰ to +36.8‰ VSMOW) and carbon (δ¹³C = −1.3‰ to +0.6‰ VPDB) isotopic signatures, confirms its authigenic origin. Siderite formed during early diagenesis of the Upper Cretaceous sandy and clayey marine sediments mobilized by mud volcanism in the area. Another assemblage, composed of dawsonite, siderite, and vein calcite (±kaolinite), represents altered arkose sandstones found as few fragments in the mud. This assemblage may be a marker of later CO₂ flooding into the sandstone aquifer in the geological past. The trace-element chemistry, particular morphology, and heavy C (δ¹³C = +5.5‰ to +7.0‰ VPDB) and O (δ¹⁸O = +39.1‰ to +39.5‰ VSMOW) isotope compositions indicate that aragonite is the only carbonate species that is related to the current MV activity. It crystallized in a shallow reservoir and was maintained by CO₂ released from rapidly ascending liquefied mud and HCO₃-Cl/Na-Mg-type of MV waters. Full article

The development of efficient spinel oxide catalysts for low-temperature oxidation of volatile organic compounds (VOCs) remains an important research objective. In this work, Ru was doped into a CoMn₂O₄ spinel to enhance its catalytic activity toward toluene oxidation and the underlying promotion mechanism of Ru doping was systematically investigated. The resulting Ru-CoMn₂O₄ catalyst showed remarkable performance, with T₉₀ reaching approximately 224 °C at a WHSV of 60,000 cm³ g⁻¹ h⁻¹ and nearly 100% CO₂ selectivity above 200 °C. Mechanism studies revealed that the reaction followed both Mars–van Krevelen (MvK) and Eley–Rideal (E–R) pathways. The reaction rates were strongly influenced by the oxidizing capacity of the catalyst, the abundance of highly valent surface species (namely Co³⁺, Mn⁴⁺, and Ru⁴⁺), adsorbed toluene, lattice oxygen, gaseous toluene, and adsorbed oxygen. With Ru doping, new Ru–O–Mn and Ru–O–Co chains formed in the CoMn₂O₄ spinel structure, leading to a moderate enhancement in oxidizing ability and a moderate increase in the concentration of highly valent surface species, adsorbed toluene, and lattice oxygen. Although a slight reduction in adsorbed oxygen was observed, Ru doping significantly boosted the overall toluene oxidation activity of CoMn₂O₄. In summary, Ru-CoMn₂O₄ represented a promising catalyst for the efficient oxidation of VOCs. Full article

Machine learning has been widely applied to phase prediction and property evaluation in multi-principal element alloys. In this work, a data-driven machine learning framework is proposed to predict the ultimate tensile strength (UTS) and total elongation (TE) of Fe-Co-Cr-Ni-Mn-Al-Ti multi-principal element alloys (MPEAs), offering a cost-effective route for the design of new MPEAs. A dataset was compiled through an extensive literature survey, and six different machine learning models were benchmarked, from which XGBoost was ultimately selected as the optimal model. The feature set was constructed on the basis of theoretical considerations and experimental data reported in the literature, and SHAP analysis was employed to further elucidate the relative importance of individual features. By imposing constraints on the screened features, two alloys predicted to exhibit superior performance under different heat-treatment conditions were identified and fabricated for experimental validation. The experimental results confirmed the reliability of the model in predicting fracture strength, and the errors observed in ductility prediction were critically examined and discussed. Moreover, the strengthening mechanisms of the designed MPEAs were further explored in terms of microstructural characteristics and lattice distortion effects. The alloy design methodology developed in this study not only provides a theoretical basis for exploring unexplored compositional spaces and processing conditions in multi-principal element alloys, but also offers an effective tool for developing novel alloys that simultaneously achieve high strength and good ductility. Full article

Micro-minerals are essential for fish, but traditional inorganic micro-minerals (IMM) have low bioavailability. This study evaluated coated inorganic micro-minerals (CIMM) in juvenile American eels under commercial recirculating aquaculture system (RAS) conditions. Three experimental groups (n = 3 tanks per group, stocking density: 138 fish/m³) were fed basal diets supplemented for 56 days with: 1000 mg/kg IMM (IMM group, providing Cu 7, Fe 200, Mn 30, Zn 70, I 1.6, Se 0.4, and Co 1.2 mg/kg diet), 1000 mg/kg CIMM (CIMM group I), or 500 mg/kg CIMM (CIMM group II). Compared to the IMM group, the CIMM group I demonstrated significantly enhanced growth performance, with the specific growth rate increasing by approximately 31.14%, higher whole-body content and retention of minerals (Ca, P, Cu, Fe, Mn, Zn), and superior intestinal health, as reflected by significantly increased activities of digestive enzymes (amylase and lipase), enhanced antioxidant capacity (elevated SOD and CAT, reduced MDA), and improved morphology (villi length and muscular thickness), an altered intestinal microbiota (increased relative abundance of Firmicutes and reduced relative abundance of Proteobacteria), and significant metabolomic alterations in purine metabolism and linoleic acid metabolism. The CIMM group II maintained growth performance, with no significant difference in WGR and SGR compared to the IMM group, while still showing significant improvements in feed intake and mineral retention (P, Cu, Fe, Zn), and antioxidant capacity. Collectively, this study not only confirms the efficacy of CIMM in commercial RAS but also reveals that the supplementation level previously shown to be effective in the laboratory (50% CIMM) is insufficient under commercial farming conditions, implying that the dietary micro-mineral requirements for juvenile American eels in commercial RAS may be higher than those established in laboratory settings. Full article

In the search for solutions to the global health threat posed by antimicrobial resistance, the development of new compounds is crucial. In this context, the in vitro testing of known indolizinoquinolinedione analogs 1–7 revealed that N,N-syn regioisomers are more active than N,N-anti regioisomers. In particular, compound 2 (ethyl 5,12-dihydro-5,12-dioxoindolizino[2,3-g]quinoline-6-carboxylate) exhibited the most significant activity against Bacillus subtilis, B. cereus, Staphylococcus aureus, and methicillin-resistant S. aureus (MRSA) bacteria. The reported increased bioactivity of metal complexes and their ability to overcome drug resistance through metal coordination have induced the study of new metal complexes of compound 2. FT-IR spectroscopy combined with DFT-simulated spectra confirmed the C=O chelation in all Zn, Cu, and Mn complexes 8–10. ESI-MS isotopic cluster analysis and UV-Vis-derived Job’s plot provided significant evidence for 1:1 chelation. Finally, ¹H NMR data were correlated to the DFT-calculated charge distribution. Complexes 8–10 displayed similar activity against B. subtilis, although this was lower than that for 2, and there were comparable effects with 2 and vancomycin antibiotic against S. aureus. FTsZ protein as a potential target of B. subtilis and DNA gyrase of S. aureus and MRSA were studied by docking calculations, revealing a good correlation with the in vitro results. Full article

As a potential strategic resource of critical metals, deep-sea cobalt-rich crusts represent one of the most promising metal reservoirs within oceanic seamount systems, and their metallogenic mechanism constitutes a frontier topic in deep-sea geoscience research. This review focuses on the cobalt-rich crusts from the Magellan Seamount region in the northwestern Pacific and synthesizes existing geological, mineralogical, and geochemical studies to systematically elucidate their mineralization processes and metal enrichment mechanisms from a microstructural perspective, with particular emphasis on cobalt enrichment and its controlling factors. Based on published observations and experimental evidence, the formation of cobalt-rich crusts is divided into three stages: (1) Mn/Fe colloid formation—At the chemical interface between oxygen-rich bottom water and the oxygen minimum zone (OMZ), Mn²⁺ and Fe²⁺ are oxidized to form hydrated oxide colloids such as δ-MnO₂ and Fe(OH)₃. (2) Key metal adsorption—Colloidal particles adsorb metal ions such as Co²⁺, Ni²⁺, and Cu²⁺ through surface complexation and oxidation–substitution reactions, among which Co²⁺ is further oxidized to Co³⁺ and stably incorporated into MnO₆ octahedral vacancies. (3) Colloid deposition and mineralization—Mn–Fe colloids aggregate, dehydrate, and cement on the exposed seamount bedrock surface to form layered cobalt-rich crusts. This process is dominated by the Fe/Mn redox cycle, representing a continuous evolution from colloidal reactions to solid-phase mineral formation. Biological processes play a crucial catalytic role in the microstructural evolution of the crusts. Mn-oxidizing bacteria and extracellular polymeric substances (EPS) accelerate Mn oxidation, regulate mineral-oriented growth, and enhance particle cementation, thereby significantly improving the oxidation and adsorption efficiency of metal ions. Tectonic and paleoceanographic evolution, seamount topography, and the circulation of Antarctic Bottom Water jointly control the metallogenic environment and metal sources, while crystal defects, redox gradients, and biological activity collectively drive metal enrichment. This review establishes a conceptual framework of a multi-level metallogenic model linking macroscopic oceanic circulation and geological evolution with microscopic chemical and biological processes, providing a theoretical basis for the exploration, prediction, and sustainable development of potential cobalt-rich crust deposits. Full article